Process for preparing acylcyclopentadienyl manganese tricarbonyl ester condensation products



United States Patent I 3,38%,l4l. Patented Mar. 7, i967 PROCESS FORPREPARING ACYLCYCLOPENTA- DIENYL MANGANESE TRICARBDNYL ESTERCONDENSATION PRODUCTS John Kozikowski, Walled Lake, Mich, and MichaelCars, Haifa, Israel, assignors to Ethyl Corporation, New York, N.Y., acorporation of Virginia No Drawing. Original application Dec. 28, 1960,Ser. No. 78,820. Divided and this application May 3, 1965, Ser. No.463,427

2 Claims. (Cl. 260429) This application is a division of parentapplication Serial No. 78,820, filed December 28, 1960. a

This invention relates to a variety of organometallic compounds and theprocesses employed in their production. More specifically, thisinvention relates to compounds and processes involving the use of anacylcyclopentadienyl manganese tricarbonyl compound.

An object of our invention is to provide new organometallic compoundsand processes for their preparation. A further object is to provideacylcyclopentadienyl manganese tricarbonyl derivatives and processes fortheir preparation. Additional Objects will become apparent from areading of the specification and claims which follow.

The objects of this invention are accomplished by reacting anacylcyclopetadienyl manganese tricarbonyl compound with an ester havingthe general formula:

In the ester reactant shown above, Y is an alkyl group containing fromone to about 8 carbon atoms and T is hydrogen or a hydrocarbon groupwhich is connected to either one or the other of the two middle carbonatoms of the ester. T can be an alkyl group, an aralkyl group, or anaryl group and can contain from one to about 18 carbon atoms. There areformed from this reaction the following products:

In the above general formulas of the reaction products, T may behydrogen. Products I, II, and III as shown above, are the half-estercondensation products of an acylcyclopentadienyl manganese tricarbonylcompound and the ester reactant as defined above. In the course of thecondensation, water is formed and this results in the hydrolysis of oneof the ester groups in the ester reactant to convert it to an acid. Tofurther illustrate this form of our invention, there are presented thefollowing examples in which all parts and percentages are by weightunless otherwise indicated.

Example I A three-necked flask equipped with a stirrer and a condenser,the top of which led to a source of nitrogen and reduced pressure, wasevacuated, fiame dried and filled with dry nitrogen. With nitrogenflowing, sodium hydride (21.6 grams) was washed into the fiask with drybenzene (200 ml.) followed by a solution of acetylcyclopentadienylmanganese tricarbonyl grams) in benzene (150 ml.). Freshly distilleddiethyl succinate (160 grams) was then added. Nitrogen flow was stoppedand the stirrer was started. A slight evolution of gas was observed fora few minutes which then stopped and during about 30 minutes of stirringno reaction appeared to take place. After that time, a sudden darkeningin color was observed and strong evolution of gas began to take place.The reaction vessel was cooled in an ice-water bath and stirring wascontinued for 1 hour until the gas evolution slowed down. The coolingbath was removed and stirring was continued for another hour at roomtemperature when the gas evolution practically ceased. The reactionmixture was then cooled again with an ice-water bath and glacial aceticacid (60 ml.) was added dropwise with vigorous stirring. This was thenfollowed by other (300 ml.) and water (200 ml.) and stirring wascontinued for another half hour. Changes in color from brown to greenand back to brown took place during the addition of the acetic acid andthe ether. The mixture was then filtered to remove about 3.5 grams of agreenish precipitate, A. The filtrate was separated into the organic andaqueous layers. The aqueous layer was washed twice with ether anddiscarded. The ether washings were combined with the organic layer andextracted with 6x250 m1. of 5 percent sodium carbonate solution, B, thenwith 4x200 ml. 5 percent potassium hydroxide solution, C. The remainingorganic layer D, was washed with 3x200 ml. water, dried over sodiumsulfate, and distilled under vacuum to recover about 65 grams of diethylsuccinate.

Example II The sodium carbonate extract, B, from Example I was acidifiedwith hydrochloric acid, extracted with ether, and the ether extract wasdried over sodium sulfate and vaporated to dryness to obtain grams of aviscous brown-reddish oil which semi-solidified on standing. Triturationwith ml. of an ether-petroleum ether solvent mixture (1:1 volume ratio)and filtration yielded 12 grams, B of yellow crystals, M.P. 100110 C.

One recrystallization from a carbon tetrachloride-benzene mixture gavecrystals with a melting point of 119- 120C.

Analysis.-Calcd. for the alkylidene half ester C H MnO- C, 51.3; H,4.01; Mn, 14.7. Found: C, 50.9; H, 3.88; Mn, 15.1 percent.

The filtrate obtained after separating the crystalline.

half ester was evaporated and the residue was triturated withether/petroleum ether (1:1 volume ratio) as before to obtain onfiltration another 12 grams of crystals, B Repeating the procedure buttriturating with carbon tetra chloride produced 2 grams of crystals, Bwhose infrared spectrum was identical with that of B Both B and Bhowever, had similar but not identical infrared spectra with B Repeatingthe CCL, procedure with the filtrate residue, there was obtained another1 gram of crystals, M.P. 245 C. (dec), B The infrared spectrum of B wasvery different from those of B B and B The filtrate from the lasttrituration was evaporated to obtain 50 grams of semi-solid yellowmaterial, B which was probably a mixture of isomeric half esters.

Example III The crystalline half ester, B grams) was refluxed withbarium hydroxide trihydrate (12 grams) in ethanol (200 ml.) and water(200 ml.) with continuous stirring for 18 hours. After cooling andfiltering, the barium salt was collected, treated with dilutehydrochloric acid and extracted with ether. The ether extract was driedover sodium sulfate and evaporated to yield 9.2 grams of crystallinematerial, M.P. 120125 C. Recrystallization from chloroform andchloroform/ether gave the analytical sample, M.P. 129130 C.

Analysis.-Calcd. for dibasic acid, C H MnO C, 48.5; H, 3.18; Mn, 15.9.Found: C, 48.8; H, 3.05; Mn, 16.1.

Example IV The crystalline compound B (10 grams) was hydro lyzed withbarium hydroxide as described above, but reflux was only for 6 hours.After work-up as before, there was obtained 13 grams of barium salt fromwhich was obtained 9.9 grams of viscous oily material, afteracidification and ether extraction.

Trituration with ether/ petroleum ether and filtration afforded 2.6grams of crystals, M.P. 148-155 C. which upon recrystallization gavecrystals of a dibasic acid having a melting point of 157158 C.

Analysis.-Calcd. for C H MnO C, 48.5; H, 3.18; Mn, 15.9. Found: C, 48.3;H, 3.11; Mn, 16.0 percent.

The filtrate from the initial trituration was evaporated to dryness, theresidue dissolved in a minimum amount of chloroform and allowed tostand. There was obtained 5.5 grams of crystals M.P. 124125 C. whichwhen recrystallized from chloroform/ether gave crystals of M.P. 129-130C., identical with the dibasic acid obtained from the hydrolysis of B inExample III.

Example V Thirty grams of the semi-solid yellow material, B referred toin Example II, was hydrolyzed in 200 ml. of ethanol and 60 ml. ofpercent potassium hydroxide and 100 ml. of water. The mixture wasallowed to stand at room temperature for 64 hours after which it wasrefluxed for 4 hours. The volume was then reduced in half, acidifiedwith hydrochloric acid and extracted with ether. The ether extract wasboiled with Norit A, filtered and dried over sodium sulfate. The extractwas then filtered again and the filtrate was heated to evaporate off theether. There was obtained 24 grams of a yellow oil which solidi- "fiedon standing. The oil was triturated with hot chloroform; the resultingsolution was allowed to stand for /2 hour and it was then filtered. Theresidue was washed with chloroform and petroleum ether to yield 8 gramsof yellow crystals having a melting point of 166-167 C. 'The crystalswere recrystallized from ether/ chloroform to give crystals having amelting point of 167-168 C. This material was another dibasic acidderivative of cyclopentadienyl manganese tricarbonyl as shown by I, II,and 111, above. On analysis, there was found: C, 48.3; H, 3.17; Mn,16.0. Calcd. for C H MnO C, 48.5; H, 3.18; Mn, 15.9 percent.

The preparation of an acylcyclopentadienyl manganese tricarbonylemployed in the process of this invention, as well as the preparation ofother related cyclopentadienyl manganese tricarbonyl compounds, is fullydescribed in our copending application Serial No. 78,820, filed December28, 1960.

Among the impontant uses of our compounds is their use as fuel and oiladditives. For example, they are useful antiknocks when added togasoline. They may be used as primary antiknocks in which they are themajor antiknock component in the fuel or as supplemental antiknocks.When used as supplemental antiknocks, they are present as the minorantiknock component in the fuel in addition to a primary antiknock suchas a tetraalkyllead compound. Typical alkyllead compounds aretetraethyllead, tetra'butyllead, tetramethyllead and various mixed leadalkyls such as dimethyldiethyllead diethyldibutyllead and the like. Whenused as either a supplemental or primary antiknock, our compounds may bepresent inthe gasoline in combination with typical scavengers such asethylene dichloride, ethylene dibromide, tricresylphosphate,trimethylphosphate and the like.

The compounds of our invention have further utility as additives toresidual and distillate fuels generally, e..g., jet fuels, home heaterfuels and diesel fuels, to reduce smoke and/ or soot formation. Also,they may be employed as additives to lubricating oils in which case theyact to improve the lubricity of the base oil. In addition, they may beemployed as additives to solid fuels to control burning rate.

Our compounds are further useful in many metal plating applications. Inorder to effect metal plating using the compounds, they are decomposedin an evacuated space containing the object to be plated. Ondecomposition, they lay down a film of metal on the object. The gaseousplating may be carried out in the presence of an inert gas so as toprevent oxidation of the plating metal or the object to be plated duringthe plating operations.

The gaseous plating technique described above finds wide application informing coatings which are not only decorative but also protect theunderlying substrate material.

Deposition of metal on a glass cloth illustrates the applied process. Aglass cloth band weighing one gram is dried for one hour in an oven atC. It is then placed in a tube which is devoid of air and there is addedto the tube 0.5 gram of bromoacetylcyclopentadienyl manganesetricarbonyl. The tube is heated at 400 C. for one hour after which timeit is cooled and opened. The cloth has a uniform metallic greyappearance and exhibits a gain in weight of about 0.02 gram.

A further utility for our compounds is as drying agents in which casethe compounds are incorporated in paints, varnish, printing inks,synthetic resins of the drying oil type, oil enamels and the like. Astill further utility for our compounds is their use as chemicalintermediates in the preparation of metal-containing polymeric materialsor in the preparation of new organic materials.

Having fully defined the novel compounds of our invention, their mode ofpreparation and their many utilities, we desire to be limited onlywithin the lawful scope of the appended claims.

We claim:

1. Process comprising reacting an acylcyclopentadienyl manganesetricarbonyl compound having the formula:

i CR

in which R is a hydrocarbon group containing from one to 20 carbon atomsand the cyclopentadienyl ring can be substituted with hydrocarbon groupscontaining from one to 8 carbon atoms with an ester having the formula:

in which Y is an alkyl group containing from one to about 8 carbon atomsand T is a hydrocarbon group containing from one to about 18 carbonatoms and which is connected to one of the 2 middle carbon atoms in theester molecule, said process being carried out in the presence of sodiumhydride as'a'condensing agent.

2. Process comprising reacting acetylcyclopentadienyl manganesetricarbonyl with diethyl succinate, said process being carried out inthe presence of sodium hydride as a condensing agent.

References Cited by the Examiner HELEN M. MCCARTHY, Acting PrimaryExaminer.

TOBIAS E. LEVOW, Examiner.

T. L. IAPALUCCI, A. DEMERS, Assistant Examiners.

1. PROCESS COMPRISING REACTING AN ACYLCYCLOPENTADIENYL MANGANESETRICARBONYL COMPOUND HAVING THE FORMULA: